Oxyalkylated amine-modified thermoplastic phenol-aldehyde resins, and method of making same



OXYALKYLATED AMlNE-MODIFIED THERMO- PLASTIC PHENOL-ALDEHYDE RESINS, AND NETHOD OF MAKING SAME Melvin De Groote, University City, Mo., assiguor to Petrolite Corporation, Wilmington, Del., a corporation of Delaware No Drawing. Application July 30, 1952, Serial No. 301,804

I 8 Claims. (Cl. 260-45) The present invention is a continuation-in-part of my co-pending application, Serial No. 288,743, filed May 19, 1952. The present invention is concerned with derivatives obtained by the oxyalkylation, particularly the oxyethylation or oxypropylation, of certain resin condensates.

These resin condensates are described in detail in the aforementioned co-pending application, Serial No.

' 288,743, and are obtained by the proces of condensing in which R is an aliphatic hydrocarbon radical having at least 4 and not more than 24 carbon atoms and substituted in the 2, 4, 6 position; (b) a basic hydroxylated secondary monoamine having not more than 32 carbon atoms in any group attached to the amino nitrogen atom, and formaldehyde; said condensation reaction being conducted at a temperature sufficiently high to eliminate water and below the pyrolytic point of the reactants and resultants of reaction; and with the proviso that the resinous condensation product resulting from the process be heat-stable and oxyalkylation-susceptible.

Compounds or derivatives are obtained by the process of oxyalkylating said amine-modified resin condensates by a member selected from the class of ethylene oxide, propylene oxide, butylene oxide, glycide and methylglycide. One aspect of the invention is, of course, the procedure for obtaining such oxyalkylation products.

In many instances and for various purposes, particularly for the resolution of petroleum emulsions of the water-in-oil type, one may combine a comparatively large proportion of the alkylene oxide, particularly propylene oxide or a combination of propylene oxide and ethylene oxide, with a compartively small proportion of the resin condensate. in some instances the ratio by weight has been as high as '50-to-1, i. e., the ultimate product of reaction contained approximately 2% of resin condensate and approximately 98% of alkylene oxide.

This invention in a more limited aspect as far as the rectants are concerned which are subjected to oxyalkylation are certain amine-modified thermoplastic phenolaldehyde resins. Such amine-modified resins are described in the aforementioned co-pending application and much that is said herein is identical with the text of said nited States Patent 0 ce Patented Apr. 24, 1956 resin condensate involved, may be'exemplified by an idealized formula as follows:

R R n R in which R represents an aliphatic hydrocarbon substituent generally having 4 and not more than 18 carbon atoms but most preferably not over 14 carbons atoms, and n generally is a small whole number varying from 1 to 4. In the resin structure it is shown as being derived from formaldehyde although obviously other aldehydes are equally satisfactory. The amine residue in the above structure is derived from a basic amine, and usually a strongly basic amine, and may be indicated thus:

RI HN/ in which R represents any appropriate carbon-linked radical such as an alkyl, alicyclic, arylalkyl radical, etc., with the proviso that at least one of the radicals designated by R has at least one hydroxyl radical. The term carbon-linked radical is intended to means a radical attached to the nitrogen atom of the above formula by a bond from a carbon atom. The hydrocarbon radical may have the carbon atom chain or equivalent interrupted by oxygen atoms. The only limitation is that the radical should not havea negative radical which considerably reduces the basicity of the amine, such as an aryl radical or an acyl radical. The introduction of two such amino radicals into acomparatively small resin molecule, for instance, one having 3 to 6 phenolic nuclei as specified, alters the resultant product in a number of ways. In the first place, a basic nitrogen atom, of course, adds a hydrophile effect; in the second place, depending on the size of the, radical R, there may be a counterbalancing hydrophobe effect or one in which the hydrophobe effect more than counterbalances the hydrophile eilect of the nitrogen atom. The presence of one or rnore hydroxyl radicals introduces a significant hydrophile efiect. Finally, in such cases where R contains one or more oxygen atoms in the form of an ether linkage another eiiect is introduced, particularly another hydrophile effect.

I am not aware that it has been previously suggested to modify resins of the kind herein described by oxyalkylation, such as oxyethylation or oxypropylation.

Referring again to the resins as such, it is worth noting 7 that combinations, either resinous or otherwise, have been prepared from phenols, aldehydes, and reactive amines particularly monoamines.

Combinations, resinous or otherwise, have been prepared from phenols, aldehydes, and reactive amines, particularly amines having secondary amino groups. Generally speaking, such materials have fallen into three classes; the first represents non-resinous combinations derived from phenols as such; the second class represents resins which are usually insoluble and used, for the purpose for which ordinary resins, particularly thermo-setting resins are adapted. The third class represents resins which are soluble as initially prepared but are not heat-stable, i. e., they are heat-convertible, which means they are not particularly suited as raw materials for subsequent chemical reaction which requires temperatures above the boiling point of water or therea'oouts.

As to the preparation of the first class, i. e., nonresinous materials obtained from phenols, aldehydes and amines,particular1y secondary 'am'i'nes,fse'e United States Patents Nos. 2,218,739 dated October 22, 1940, to Brusqn; 2,033,092 dated,March 3 1936 to Bruson; and Q 6, l, f 1 t 9.A1307 93, 1 1.

fAfsto" afprocejdur'e bfy whiche resin; is profit cdaslsuch involving all three reactantsand generally jresultingfjin an insoluble resin, or in any ev'ntfa resin which'becornes insoluble in presence of added formaldehyde. or the like, see United States'Patents Nos. 2,34.1,9Q7,dated February 15, l944,"to 'Cheetham 'et"al.;,2,122,433, dated ,July 5, 1938, to Meigs; 2,168,335, dated August 8, 1939, to Heckert; 2,098,869, dated November 9,1937, to Harmon et al.; and 2,211,960, dated August 20, 1940, to Meigs. ,A thirdelass ofrnaterial which approaches the ciosest to the herein' described derivatives, or resinous amine derivatives isdescribed'inU. S Patent No. 2,031,557, dated February 18, 1936, to Bruson. l

, The resins ernployed asrawmaterials in thein'stant procedureare characterized by the presence of an aliphatic radicalin'the .orthqor paraposition, i. e., the phenols themselves are difunctiotialphenols. This is a differentiation from the ,lresin's described in the aforementioned Bruson patent, 'No. 2,031,557, insofar thatsaid patent discloses suitable resins obtained from meta-substituted phenols, hydroxybenzene, res'orcinol, p,p(dihydroxydiphenyD-dimethylmethane, and the like, all of which have at leastthree points of reaction per ph nolic nuclei and as a result can yield resins which may be 'at least incipiently 'crossflinked even thoughthey'are apparentlyfstill soluble in oxygenated organic solvents "or 'else are'heat-reactive insofar that theyf 'n'ay approach insolubility or become insoluble due to the effect of heat, or'added' formaldehyde, oribd h... h .l. Y,

H A The resins herein employed contain "only two terminal ,gro'pps which are'reactive to fofrmaldehydef'i. e., they are jdifhnctional' from thels'taiidp ointof "methylol-forming re- A We l n a th h "on l S art t nctional phenols, and depending on the procedure l t ploy ll"Q 1 1 lfiay' b' in C bss link liswhi b, n ica e thatone or'rnorejof e phenolicnuclei'havefbeeneonthemole cu le as a whole fshift can'take place afterj'the resin has been formed or dut es? r i f rmat q Br fly. n e p e si y Twh'ere analltyl radical, as frnethyl, ethyl, propyl,

bfutyl, or the like, shifts fromfanorthoposition to a meta positiomjor from a'par'a position to afrn'etaposition, For

in'stanca'in the case ofphenol-aldehyde varpish resins,

one can prepareat least'some in which the fesihsinstead of having onlytwo points of reaction can have three, and

' possibly more points of reaction, with formaldehyde, or any other reactant whichtends to form a rnethylol or sub- 'stituted methylol group.

Apparently there is no similar limitation in regard to the resins employed in the aforementioned Bruson Patent 2,031,557, for the reason that one may prepare suitable resins from phenols of the kind alreadyspecified which invariably and inevitably would yield a'resin havin'g a functionality greater than two in the ultimate resin mole cule. M ,The resins herein einploye'd are soluble in a 'non- 'oxygenated hydrocarbon solvent, 'such as benzene or xylene.

a way as to render them hydrocarbonsoluble, i. e., soluble inbenzene. Theoriginal resins of U. S. Patent 2,031 ,557

are selected on the basis of solubility in an oxygenated inert organic solvent, such as alcohol orjdioxan e. ."Itis immaterial whether the resins herejemployecl aresoluble in dioxane or alcohol, but they'must be soluble in benzene.

The resins herein employedas raw materials must be comparatively low molalproducts having on'the average 3 to 6 nuclei per resin molecule. The resins employed in 4 the aforementioned U. S. Patent No. 2,031,557, apparently need not meet any such limitations.

The condensation products here obtained, whether in the form of the free base o r the salt, do not go over to the insoluble stage on heating. This apparently is not true of the materials described in aforementioned Bruson a en 2 31, 7 and. ppa en y t e of h Q i with which the invention is concerned, is to obtain a heatconvertible condensation product. p The condensation product'obtained aizcordingtothe present. invention is heat stable and,,"in'fact, one ofits outstandingqualitics is that it can tie-"subjected to oxyalkylation, particularly oxyethylation or oziypropylation, under conventional conditions, i. e., presence'of an alkaline catalyst, for example, but in any event at a temperature above C. without becoming an insoluble mass.

Although these condensation products have been preparedprim'arily with tliehthought in mind that they are preoursors for subsequent reactiomyet as'such and without further reaction, they have definitely valuable properties and usesashereinafter pointed out.

What has been said previously in regard to heat stability, particularly when employed as a reactant for preparation ofderivatiy'es, islst'illfirnportant from the standp oint of manufacture of the condensation-products themselves in- 'jsofantliat inthe condensation process employed in preparingthecotnpo nds described subsequently in detail, there'is'no objection -to the employingof'a temperature above the boiling point of water. As a matter of fact, all 'the"'example's included subsequently employ temperatures "going up to to C, If one were using resins of theikind described in U. '8. Patent No. 2,031,557 it" appears desirable and perhaps absolutely necessary that the "temperature befkept relatively low, for instance, between;2'o'c;and'1o0? 'C., and more specifically at a temperature "of 80""to 90 C. There is nosuch limitation in the condensation procedure horein described for reasons which are obvious in light'of what has been said previously.

What is said above deserves further amplification at this point for the reason that it may shorten What is said subsequently in regard to the production of the herein dei e i etlsqntle a i n Pro u t sps te out in the I stant inyenti on the resin selected is xylene or benzene soluble, which v differentiates the resins from those em- ,ployed iplthe aforementioned Bruson Patent No. 2,031,- .557 ,Si c m qnnal ehy e ene y. is employed ewe nornicallyin an aqueous phase (30% to 40% solution, for

example) it is necessary to have manufacturing procedure whichwill allow reactions to take place at the interface ofthe two immiscible liquids, to wit, the formaldehyde solution and the resin solution, on the assumption that generally the amine will dissolve in one phase or the other. Although reactions of the kind herein described will begiu ,at'least .at comparatively low temperatures, for instance, 30 Q, 40f Q, or 50 C., yet the reaction does ,not, ultimately 'the temperature must still pass within the zoneindicated elsewhere, i. e., somewhere above the boiling'point, of water unless some obvious equivalent procedure is used. I,

Any reference, as in ,thehereto appendedelaims, to the procedure employed in the process is not intended to limit themeth'od or order inwhich the reactants are added,

fc ommingle d or reacted. The procedure has been referred j to as 'a"conc'1ensation process for obvious reasons As pointed out elsewhere it' ismy preference to dissolve the resin in a suitable solvent, add the amine, and then add the formaldehyde as a 37% solution. However, all three reactants can be added in any order. I am inclined to believe that in the presence of a basic catalyst, such as the amine employed; that the formaldehyde produces methylol groups attached to the phenolic nuclei which, in turn, react with the amine. It would be immaterial, of course, if the formaldehyde reacted with the amine so as to introduce a methylol group attached to nitrogen which, in turn, would react with the resin molecule. Also, it would be immaterial if both types of compounds were formed which reacted with each other with the evolution of a mole of formaldehyde available for further reaction. Furthermore, a reaction could take place in which three different molecules are simultaneously involved although, emulsification test includes such obvious variant. for theoretical reasons, that is less likely. What is said Reference is again made to U. S. Patent 2,499,368 dated herein in this respect is simply by way of explanation to March 7, 1950, to De Groote and Keiser. In said immeavoid any limitation in regard to the appended claims. diately aforementioned patent the following test appears: Allowing for the fact that the nitrogen radical contains The same is true in regard to the oxyalkylated resins at least one hydroxyl the condensate can be depicted more herein ifi d ti l l in the lower stage f satisfactorily the Present P p in the following alkylation, the so-called sub-surface-active stage. The manner: surface-active properties are readily demonstrated by producin a x lene-water emulsion. Suitable procedure is as H OH H I OH OH H (OH) follov s: Tl ie oxyalkylated resin is dissolved in an equal N4 weight of xylene. Such 50-50 solution is then mixed with H H (H0).,-R' axon ,1 1-3 volumes of water and shaken to produce an emulsion. The amount of xylene is invariably sufficient to reduce R R n R even a tacky resinous product to a solutionwhich is readily in which the characters have their previous significance, 3U dispersible. The emulsions so produced are usually and is the integer 0 Or a small Wh1e m1mbeI, with the xylene-in-water emulsions (oil-in-water type) particularly PTOVisO that in each terminal amino Tadlcal theremust be when the amount of distilled water used is at least slightly atleast one hydroxyl groupin excess of the volume of xylene solution and also if Thus one can Showman oxyalkylatlon can take shaken vigorously. At times, particularly in the lowest not only at thephenohc hyfiroxyl but also at the ammo stage of oxyalkylation, one may obtain a water-in-xylene group hydroxyl 1n the followlng manner:

(RO),vH (R"O), H (RO)'H R t) l R'o(R' 'o),'H

2- H(0R)n OR H R R R n R I I in which for simplicity the formula just shown previously emulsion (wate yp which is p to reverse on has been limited to the specific instance where there is e V g Shaking and further dilution With Wateronly one hydroxyl in the amino radical. In the above f in doubt as to this P p y, Comparison With arrsstl'l formula RO is the radical of alkylene oxide, such as the obtained from para-tertiary butylphenol and formaldehyde ethoxy, propoxy or similar radicals derived from glycide, (ratio 1 part phenol to 1.1 formaldehyde) using an acid ethylene oxide, propylene oxide, or the like, and n is a catalyst and then followed by oxyalkylation using 2 moles number varying from 1 to 60, with the proviso that one of ethylene oxide for each phenolic hydroxyl, is helpful. need not oxyalkylate all the available phenolic hydroxyl Such resin prior to'oxyal y has a 111016611181" Wight radicals or all the available hydroxyls which are part of indicating a t 4 /2 units p r resin molecule h resin, the amino radical. In other words, one need convert only h diluted With all equal Weight of y Will serve to two hydroxyl radicals per condensate unit. It is imillustrate the above emulsification test. material whether they are phenolic hydroxyls or hy- In a few instances, the resin y not be sufficiently droxyls which are part of the amino radical. Stated ansoluble in xylene alone but may require the addition of other way, u can be zero as well as a whole number subsome ethylene glycol diethylether as described elsewhere. ject to wht has been said immediately preceding, all of t is understood that Such miXture, ny er Similar which will be considered in greater detail subsequently. mixture, is considered the equivalent of xylene for the pur One important use of the herein described products is pose of this test. in the resolution of petroleum emulsions of the water-in- In many cases, there is no doubt as to the presence or oil type. absence of hydrophile or surface-active characteristics in As far as the use of the herein described products goes' the products used in accordance with this invention. They for purpose of resolution of petroleum emulsions of the dissolve or disperse in water; and such dispersions foam water-in-oil type, I particularly prefer to use those which readily. With border-line cases, i. e., those which show as such or in the form of the free base or hydrate, i. e., only incipient hydrophile or surface-active property (subcombination with water or particularly in the form of a surface-activity) tests for emulsifying properties or selflow molal organic acid such as the acetate or hydroxy dispersibility are useful. The fact thatareagent is capable acetate, have sufficiently hydrophile character to at least of producing a dispersion in water is proof that it is dismeet the test set forth in U. S. Patent No. 2,499,368, tinctly hydrophile. In doubtful cases, comparison can be dated March 7, 1950, to De Groote et al. In said patent such test for emulsification using a water-insoluble solvent, generally xylene, is described as an index of surface activity.

In the present instance the various condensation products as such or in the form of the free base or in the form of the acetate, may not necessarily be xylene-soluble althoughthey are in many instances. If such compounds are not xylene-soluble the obvious chemical equivalent or equivalent chemical test can be made by simply using some suitable solvent, preferably a water-soluble solvent such as ethylene glycoldiethylether, or a low molal alcohol, or a mixture to dissolve the appropriate product being examined and then mix with the equal weight of xylene, followed by addition of water. Such test is obviously the same for the reason that there will be two phases on vigorous shaking and surface activity makes its presence manifest. It is understood the reference in the hereto appended claims as to the use of xylene in the made with the butylphenol-formaldehyde resin analog wherein 2 moles of ethylene oxide here been introduced for each phenolic nucleus.

The presence of xylene or an equivalent water-insoluble solvent may mask the point at which a solvent-free product For this reas om if it is desirable to determine the approximajte point where self emulsification begins, then itis better to eliminate the xylene or equivalent trom a small poremulsifying properties and go through the range of ho- 'mogeneous"dispersibility or admixture with water even in presence of added water-insoluble solvent and minor proportionsof 'comm'on electrolytes as occur in oil field brines.

Elsewhere, it ispointed'outthat an emulsification test may be used' todetermine ranges of surface-activity and that such 'emulsification tests employa xylene solution. Slated another way, it is really immaterial whether a xylene solution produces a sol or whether it merely produces an emulsion? H p A l ufi v sv s ri d h i ent o ri dn tn se ,sari ly irrits most complete aspect, the text immediately following will be a more complete descriptionwith specific reference to reagents and the method of manufacture.

For convenience the subsequent text will be divided into five parts; 7 r M Part 1 is concerned with the general structure ofithe amine-modifiedresin condensates and also theresin itself,

which isus'ed as a raw material;

Part 2 is concerned with'appropriate basic secondary 1 monoamines containing at least one hydroxyl radical which may be employed in the preparation of the herein described amine-modified resins or condensates;

Part 3 is concerned with the condensation reactiohshnvolving the resin, the amine, and formaldehyde to produce the specific products or compounds;

Part 4 is concerned With the oxyalkylation of the products described in Part 3, preceding; and ,Part, 5 is concerned with uses for the products outlined in Pa .,prs e ns-s In the subsequent text, Parts 1, Land 3 appear insubstantially the sameform as in the text of aforementioned coI-pendingapplication, Serial No. 288,743, filed May 19, 1952, for both purpose of convenience and comparison.

PART 1 It is well known that one canreadily purchase on the open market, or prepare, fusible, organic solvent-soluble. water-insoluble resin polymers of a composition approximated in an idealized form by the formula In the aboveifdrmula' n represents a small whole number varying from 1 to 6, 7 or 8, or more, up to probably 10 k or 2 units, particularly when the resin is subjected to I "under: a vacuum as described in the literature. "A

radialiliayiiigfrtim t MQcarbon atoms, sutih e5 5 butyl, fiy ,iiex liga'eje i raoneeyi radical, "Where thedivalent bridge radical is'shown'as beingflderived from formaldeli'tdeit niayfof 'c'ouisqbe derived from any other reactive zildehyde navmgs carbon atoms'or less.

Becausea resin jo'rgan'ie'solvei t soluble does not mean it is'necessai fiysoluble'in any organic solvent. This is particularly"triief'where the resins are derived from 'trifunctional phenols as previously noted. However, even when obtained from adifhiictibnal phenoLtor instance para-phenylphenol, one may obtain a resin which is not soluble in a nouoxygeiiated 'so'lvenh'such as benzene, or xylene, but requires an"oxyglena'ted solvent such'as' a low molal alcohol, "dioxane, 'or diethylglycol diethylether. Sometimes a mixture of the two solvents (oxygenated and nonoxygenated) will serve. 'See Example 9a of U. S. Patent No. 2,499,365, dated March 7, 1950, to De Groote and Keiser. I I g r The resins herein employed as raw materials must be soluble in a nonoxygenated solvent, such as benzene or xylene. This presents no problem insofar that all that is required is to make a solubility test on commercially available resins, or else prepare resins which are xylene or benzene-soluble as described in aforementioned U. 5. Patent No. 2,499,365, or in U. S. Patent No. 2,499,368

datcd March 7 l950,to De Groote and Keiscr. In said i patent there are described oxyalkylation-susceptible, fusible, nonoxygenated-organic "solvent-soluble, water-insoliible, low-stage'pheiiol aldehyde resins'having an aver age melecularweight corresponding to at least 3 and not over-'6 pheiitilieriucl'ei per resin molecule; said resin being difunctional onlyin regard to methylol-forming reactivity; said, resin being derived'by reaction between a difunction al iiibnohydric phenol andf an aldehyde having not over 8 carbon atomsaridie'ac'tive towardsaid phenol; said resin being formed in'-the substantial absence of trifunctional phenols; said phenol being of the formula in which R is an aliphatic hydrocarbon radical having at "least 4ita'r'bon atoms and not more than 24 carbon atoms, and substituted in the 2,4,6 position.

v If one selected a resin of the kind just described previously and reacted approximately one mole of the resin with twofmolesof formaldehyde and two moles of a basic nonhydroxylated secondary amine as specified, folloviingthe' same idealized over-simplification previously referred to, the resultant product might be illustrated thus:

R n R The"basic'h'ydroxylated amine may be designatedthus:

R! Hui U "lrifcondi1ctingfeaictions'of this kind one does not nec- "es's'arily obtain a hundred per cent yield for obvious reasons Qertain side reactions may talre place. For instance, Z'ifidl'es of' amine may combinewith one "mole V amine in the reaction on r on on n i n H n 1% H 1% As has been pointed out previously, as far as the resin unit goes one can use a mole of aldehyde other than formaldehyde, such as acetaldehyde, propionaldehyde or butyraldehyde. The resin unit may be exemplified thus:

in which R is the divalent radical obtained from the particular aldehyde employed to form the resin. For reasons which are obvious the condensation product obtained appears to be described best in terms of the method of manufacture.

As previously stated the preparation of resins, the kind herein employed as reactants, is well known. See previously mentioned U. S. Patent 2,499,368. Resins can be made using an acid catalyst or basic catalyst or a catalyst having neither acid nor basic properties in the ordinary sense or without any catalyst at all. It is preferable that the resins employed be substantially neutral. In other words, if prepared by using a strong acid as a'catalyst, such strong acid should be neutralized. Similarly, it a strong base is used as a catalyst it is preferable that the base be neutralized although I have found that some-. times the reaction described proceeded more rapidly in the presence of a small amount of a free base. The amount may be as small as a 200th of a percent and as much as a few 10ths of a percent. Sometimes moderate increase in caustic soda and caustic potash may be used. However, the most desirable procedure in practically every case is to have the resin neutral.

In preparing resins one does not get a single polymer, i. e., one having just 3 units, or just 4 units, or just 5 units, or just 6 units, etc. It is usually a mixture; for in stance, one approximating 4 phenolic nuclei will .have some trimer and pentamer present. Thus, the molecular 10 weight may be such that it corresponds to a fractional value for n as, for example 3.5, 4.5 or 5.2.

In the actual manufacture of the resins I found no reason for'using other than those which are lowest in price and most readily available commercially. For purposes of convenience suitable resins are characterized in the following table:

TABLE I Mol wt Ex. Position R' derived R n of resin No. of R from molecule Nonyl Para. 4.8 1, 570. 4 3. 5 882. 5 3. 5 882. 5 3. 5 1, 02s. 5 3. 5 959. 5 Mixed secondary 3. 5 805. 5

and tertiary amyl.

3. 6 805. 5 3. 5 1, 036. 5 3. 5 1, 190. 5 3. 5 1, 267. 5 3. 5 1, 344. 5 3. 5 1, 498. 5 3. 5 945. 5 3. 5 1, 022.5 3. 5 1, 330. 5 3. 5 1, 071. 5 3. 5 1, 148. 5 onyl 3. 5 1, 456.5 Tertiary butyi. 3. 5 1, 008.5

2011... Tertiary amyl..... ..do .-do 3. 5 1, 085. 5 21a Nonyl do do 3.5 1,393.5 22a Tertiary butyL--. do..-. Formaldehyde. 4. 2 996. 6 23a... Tertiary amy1 do ..do 4.2 1, 083:4 24a-.. N v1 4. 2 1, 430. 6 4. 8 1, 094. 4 4. s 1,189.6

PART 2 As has been pointed out previously the amine herein employed as a reactant is a basic hydroxylated secondary monoamine whose composition is indicated thus:

in which R represents a monovalent alkyl, alicyclic, arylalkyl radical which may be hetei'ocyclic in a few instances as in a secondary amine derived from furfurylamine by reaction of ethylene oxide or propylene oxide. Furthermore, at least one of the radicals designated by R must have at least one hydroxyl radical. A large number of secondary amines are available and may be suitably employed as reactants for the present purpose. Among others, one may employ diethanolamine, methyl ethanolamine, dipropanolamine and ethylpropanolamine. Other suitable secondary amines are obtained, of course, by taking any suitable primary amine, such as an alkylamine, an arylalkylamine, or an alicyclic amine, and treating the amine with one mole of an oxyalkylating agent, such as ethylene oxide, propylene oxide, butylene oxide, glycide, or methylglycide. Suitable primary amines which can be so converted into secondary amines, include butylamine, amylamine, hexylamine, higher molecular weight amines derived from fatty acids, cyclohexylamine, benzylamine, furfurylamine, etc. In other instances secondary amines which have at least one hydroxyl radical can be treated similarly with an oxyalkylating agent or, for that matter, with an alkylating agent such as benzylchloride, esters of chloroacetic acid, alkyl bromides, di-

the primary amine intoa secondaryamine. -Ahiong others, such amiries include 2-amiiio 1 butanol,=-2-amino- Q-aminO-Z-ethyI-1,3-propai1edio1, and i trie-(hydroxymethonaooimm CHr-CH: ou rr-cmocrnoonefinr Such haloalkyl eth'ers "can be reacted with ammonia or with a primary amine, such as ethanolamine, propanolamine, monoglycerylamine, etc., to produce a' secondary amine in which thereis' not only present a-hydr'oxyl radical but a repetitious ether'linkage. Compounds can be readily obtained which are exemplified by the following formulas: I

(CiHsO CiHt) (C H9O CHzCH(CHa) 0 (CH2) CHCH?) /NH HO 0 H;

onzoemomoonlomodnlom cnaoomomonionionzom) /HH B00111,

or comparable compounds having two" hydroxylat'ed groups of difierentlengths as is HooHlonmoH-lomoombm) HOCaHi Other examples of suitable amines' include be'nzyle'th'a'nolamine and methylethanolamine; also amines obtained by treating cyclo'hexylmethylamine"with one mole of'an" ox alkylating agent as previously-described; beta-'ethylhefiiylairline when is of particular iiitrest becatise it ineludes 12 'a 4 very definite hydrophile group includes sugar amines such as glucainine, 'gelacta'mine and fruc'tamine, such as "N hydroityethyl'glucamine, N methylglucamine, 'N hy- 'droxyethylgalactamine, and N-hydroxyethylfructamine Other suitable amines may be illustrated by CH: HO.CH2.CHzOH NH HO.CH2 .C.OHaOH CH; CH AJ .GHQOH NH CHaLCHiOH See, also, corresponding hydroxylated amines which can be obtained from rosin or similar raw materials and described in U S. Patent No. 2,510,063, dated June 6, 1950) to Bried. Still other examplesare illustrated by treatmentof certain primary amines, such as the following; with a mole of an oxyalkylating agent as described; phenoxyethylarnine, phenoxypropylamine, phenoxyalphaniethylethylamine, and phenoxypropylamine.

Other procedures for production of suitable compounds having a hydroxyl group and a single basic amino nitrogen aterncanbe'obtained from any suitable alcohol or the like by reactionwith a reagent which contains an epoxide group end a -secondary amine group. Such reactants are described; forexamp'le, in U. S. Patents Nos. 1,977,251 and 1,977,253, both dated October 16, 1934, to Stallmann. Among the reactants described in said latter patent are the following:

ore-crr bm-un-cm-omon C FjGE-om-zrm-om-wnoran-0mm;

"PART 3 The pfodnctsobtained by'the herein described processes represent 'cogenericmixtures'which are the result of a "condensation reaction or reactions. Since the resin molecule cannot bedefined satisfactorily by formula, although it n'iay be*so illustrated in an idealized simplification, -it is diificult to actually depict thefinal product of the cogeneric mixture" except in terms of the process itself.

Previous reference has been made to the fact that: the procedure here'inemploy'edis comparable, in. a general way, tothat-whi'ch corresponds to somewhat similar derivativesmade'either fronrphenols as dilierentiated from a resin,--or-- in the manufacture of a phenol-amine-aldehyde resin; orelsefrom a particularly selected resin and .an amine and formaldehyde in the manner described in Brus'on Patent No; 2,031,557 in order to obtain a heat-reactive resin. Since the condensation products obtained are not heat-convertible and" since manufacture is not restricted to asingle phase system,"and since temperatures up to 150 C. or thereabouts'may be employed, it is "obvious thatthe procedure-becomes comparatively simple. indeed? perhaps no' description is necessary over and above whaehas been said previously, in light of subse- 'quent exarn'ples. However, 'forpurpose of clarity the follow-ihg details are included.

nomical.

A convenient piece of equipment for preparation of these cogeneric mixtures is a resin pot of the kind described in aforementioned U. S. Patent No. 2,499,368. In most instances the resin selected is not apt to be a fusible liquid at the early or low temperature stage of reaction if employed as subsequently described; in fact, usually it is apt to be a solid at distinctly higher temperatures, for instance, ordinary room temperature. Thus, I have found it convenient to use a solvent and particularly one which can be removed readily at a comparatively moderate temperature, for instance, at 150 C. A suitable solvent is usually benzene, xylene, or acomparable petroleum hydrocarbon or a mixture of such or similar solvents. Indeed, resins which are not soluble except in oxygenated solvents or mixtures containing such solvents are not here included as raw materials. The reaction can be conducted in such a way that the initial reaction, and perhaps the bulk of the reaction, takes place in a polyphase system. However, if desirable, one can use an oxygenated solvent such as a low-boiling alcohol, including ethyl alcohol, methyl alcohol, etc. Higher alcohols can be used or one can use a comparatively non-volatile solvent such as dioxane or the diethylether of ethyleneglycol. One can also use a mixture of benzene or xylene and such oxygenated solvents. Note that the use of such oxygenated solvent is not required in the sense that it is not necessary to use an initial resin which is soluble only in an oxygenated solvent as just noted, and it is not necessary to have a single phase system for reaction.

Actually, water is apt to be present as a solvent for the reason that in most cases aqueous formaldehyde is employed, which may be the commercial product which is approximately 37%, or it may be diluted down to about 30% formaldehyde. However, paraformaldehyde can be used but it is more difficult perhaps to add a solid material instead of the liquid solution and, everything else being equal, the latter is apt to be more eco- In any event, water is present as water of reaction. If the solvent is completely removed at the end of the process, no problem is involved if the material is used for any subsequent reaction. However, if the reaction mass is going to be subjected to some further reaction where the solvent may be objectionable, as in the case of ethyl or hexyl alcohol, and if there is to be subsequent oxyalkylation, then, obviously, the alcohol should not be used or else it should be removed. The fact that an oxygenated solvent need not be employed, of course, is an advanatge for reasons stated.

Another factor, as far as the selection of solvent goes,

is whether or not the cogeneric mixture obtained at they end of the reaction is to be used as such or in the salt form. The cogeneric mixtures obtained are apt to be solids or thick viscous liquids in which there is some change from the initial resin itself, particularly if some I of the initial solvent is apt to remain without complete removal. Even if one starts with a resin which is almost water-white in color, the products obtained are almost invariably a dark red in color or at least a red-amber or some color which includes both an amber component and a reddish component. By and large, the melting point is apt to be lower and the products may be more sticky and more tacky than the original resin itself. Depending on the resin selected and on the amine selected the condensation product or reaction mass on a solventfree basis may be hard, resinous and comparable to the resin itself.

The products obtained, depending on the reactants selected, may be water-insoluble or water-dispersible, or water-soluble, or close to being water-soluble. Water solubility is enhanced, of course, by making a solution in the acidified vehicle such as a dilute solution, for instance, a solution of hydrochloric acid, acetic acid, hydroxyacetic acid, etc. vOne also may convert the fin ished product into salts by simply adding a stoichiometric 14 amount of anyselected acid and removing any water present by refluxing with benzene or the like. In fact, the selection of the solvent employed may depend in part whether or not the product at the completion of the reaction is to be converted into a salt form.

in the next succeeding paragraph it is pointed out that frequently it is convenient to eliminate all solvent, using a temperature of not over C. and employing vac uum, if required. This applies, of course, only to those circumstances where it is desirable or necessary to remove the solvent. Petroleum solvents, aromatic solvents, etc., can be used. The selection of solvent, such as benzene, xylene, or the like, depends primarily on cost, i. e., the use of the most economical solvent and also on three other factors, two of which have been previously mentioned; (a) is the solvent to remain in the reaction mass without removal? (b) is the reaction mass to be subjected to further reaction in which the solvent, for instance, an alcohol, either low boiling or high boiling, might interfere as in the case of oxyalkylation? and the third factor is this, (0) is an effort to be made to purify the reaction mass by the usual procedure as, for example,

a Water-wash to remove the water-soluble unreacted' formaldehyde, if an or a water-wash to remove any unreacted low molal soluble amine, if employed and present after reaction? Such procedures are well known and, needless to say, certain solvents are more suitable than others. Everything else being equal, I have found xylene the most satisfactory solvent.

I have found no particular advantage in using a low temperature in the early stage of the reaction because, and for reasons explained, this is not necessary although it does apply in some other procedures that, in a general way, bear some similarity to the present procedure. There is no objec'tion, of course, to giving the reaction an opportunity to prweed as far as it will at some low temperature,-for instance, 30 to 40 but ultimately one must employ the higher temperature in order to obtain products of the kind herein described. If a lower temperature reaction is used initially the period is not critical, in fact, it may be anything from a few hours up to 24 hours. I have not found any case where it was neces sary or even desirable to hold the low temperature stage for more than 24 hours. In fact, I am not convinced there is any advantage in holding it at this stage for more than 3 or 4 hours at the most. This, again, is a matter of convenience largely for one reason. In heating and stirring the reaction mass there is a tendency for formaldehyde to be lost. Thus, if the reaction can be conducted at a lower temperature, then the amount of unreacted formaldehyde is decreased subsequently and makes it easier to prevent any loss. Here, again, this lower temperature is not necessary by virtue of heat convertibility as previously referred to.

If solvents and reactants are selected so the reactants and products or" reaction are mutually soluble, then agitation is required only to the extent that it helps cooling or helps distribution of the incoming formaldehyde. This mutual solubility is notnecessary as previously pointed out but may be convenient under certain circumstances. On the other hand, if the products are not mutually soluble then agitation should be more vigorous for the reason that reaction probably takes place principally at I the. interfaces and the more vigorous the agitation the more interfacial area. The general procedure employed v is invariably the same when adding the resin and the selected solvent, such as benzene or xylene. Refluxing should be long enough to insure that the resin added,

preferably in a powdered form, is completely soluble.

However, if the resin is prepared as such it may be added in solution form, just as preparation is described in aforementioned U. S. Patent 2,499,368. After the resin is in complete solution the amine is added and stirred. Depending on the amine selected, it may or may not be soluble in the resin solution. If it is not soluble in the resin would be extremely unusual.

'is then added in a suitable form. For reasons pointed out Iprefer to usea -solution=and whethei' to use a commercial-37% concentration is simply.a matter of choice. In large scale manufacturing there maybesome ad- 'vantagein using a 30%.solutionif formaldehyde but apparen'tly'this is'not true-on=a small laboratory scale or pilot plant sc'ale. '30% formaldehydemay tend to decrease any' forrnaldehyde loss or make it easier to control unreacted formaldehyde loss.

On a large scale if there is any' 'difficulty. with formaldehyde. loss control, one can use a=moredilute form of formaldehydefor instance, a 30% solution. The reaction can be'conducted in an autoclave and no attempt made to remove water until thereaction is over. Generally speaking, such. a procedure is mucli less satisfactory for a number of reasons. 3 For example, the reaction does not seem togo to completion, foaming takes place, and other mechanicalor chemicaldifliculties are involved. I- have found no advantage in usingsolid formaldehyde-because evenherewater of reaction is formed.

'Returning again to the preferred method-of reaction and particularly from the standpoint-of laboratory procedure employing a glass resin pot, Whenthe reaction has proceeded as one can reasonablyexpect at a low'temperature; forinstance, after holding-thereaction mass with or without stirring, dependingon whether or not his homogeneous, at 30 or 40 C;for'4; or 5, hours; or at the most, up to -24. hours, I then complete-the reaction by raising the temperature up to 150 C., orgthereabouts as required. The initial low temperature procedure canbe eliminated or reduced to merely the shortestperiod of time which avoids loss of amine or formaldehyde. At a higher temperature I use a phase-separating trap and subject'the mixture to reflux condensation until the water of reaction and the water of solution of theformaldehyde is eliminated. I then permit'the temperature to rise to somewhere about 100 C., and generally slightly above 100 C., and below 150 C. by .eliminatingthe solvent or part of the solvent so the reaction mass stays within this predetermined range. This periodofheating and refluxing, after the water is eliminated, is continued until the reactionmass is homogeneous. and then for one to three hours longer. The removal of. the solventsis con- .ducted in a conventional, mannerinthesame way as the removal of solvents in resin manufacture asdescribed. in aforementioned U. S. Patent No 2,499,368.

Needless to say, as .far as the ratio of reactants goes I have invariably employed approximately one mole of the resin based on the molecular weight of the resin molecule, 2 moles of the secondary amine and 2 moles .of formaldehyde. In some instances I have added atrace of caustic as an added catalyst but, have found no vparticular advantage in this. In other cases I haveused a, slight; excess of formaldehyde and, again, have not found any particular advantage in this. excess of amine and, again, have not found any particular advantage in so doing. Whenever feasible I have checked the completeness of reaction in the usual ways, including the amount of water of reaction, molecular weight,--and particularly in some instances have checked Whether or not the end productshowed surface-activity, particularly in a dilute acetic acid solution. The'nitrogen content after removal of unreacted amine; if'any is present, is another index.

In othercases I have used a slight.

1 Example lb The phenol-aldehyde resin is theone that has been identified: previously as Example 211. It was obtained from a paratertiary butyl phenol andtormaldehyde. The resin was prepared using an acid catalystwhich was completely neutralized at the end offthe reaction. The molecular weight of the resin was 882.5. This corresponded to an average of about 3 /2 phenolic nuclei, as the value for n whichexcludes'the 2 externalnuclei, i. e., the resin was largely a mixture having 3 nuclei-and 4 nuclei excluding the 2 external nuclei, or 5 and 6 overall nuclei. The resin so obtained in a neutral state had a light amber color.

882 grams of, the resinidentified as 2a preceding were powdered and mixed with 700, grams of xylene. The mixturewas refluxed until solution was complete. It was then adjusted to approximately 30 to C. and 2l0 grams of diethanolamine added. The mixture was stirred vigorously and formaldehyde added slowly. The formaldehyde used was a 37% solution and 160, grams were employed which were addedinabout 3 hours. The mixture was stirred. vigorously and kept within a temperature range of 30 to C.' for about Zlhours. At the end of this period of time it was refluxed, using a phase-separating trap and a small amount of aqueous distillate withdrawn from, time to time and the presence. of unreacted formaldehyde noted. Any unreacted formaldehyde seemed to disappear within approximately 3 hours after the refluxing was started. As soon as the odor of formaldehyde was 1 In the hereto attached claims reference is-made to=thev no longer detectible the phase-separating trap was set so as to eliminate all water of solution and reaction. After the water was eliminated part ofthe xylene was removed until thetemperaturereached about ,150" C. The mass was kept at this highertemperature for about 3% hours and reaction stopped. During this time. an additional water, which was probably water of reaction which had formed, was eliminated by means of the trap. The residual xylene was permitted to stayin the cogeneric mixture. A small amount of the sample was heated on a water bath to removethe excess xylene and the residual material was dark red in color and hadthe consistency of asticky fluid or a tackyresin. The overallreactiontime was a little over30 hours. In-other instances it has varied from approximately 24 to 36 hours. The time can be reduced by cutting the low temperature period to about 3 to 6 hours.

Note that in Table II following there are a large number of added examples illustrating the same procedure. In each ;case the initial mixture was stirred and held at a fairly low temperature (30 to 40 C.) for a period of ,several hours. ,Then refluxing-was employed until the odor of formaldehyde disappeared. After theodor of formaldehyde disappeared thephase-separating trap, was employed to separate out all the water, both the solution and condensation. 1 After all the water hadbeen separated enough-xylene was taken out to have the final product reflux for several hours somewhere in the range of to C., or the *eabouts. f "Usually the mixture yielded a clear'solution by the time the bulkof the water, or all of the water, had been removed.

Note that-as pointedout previously this procedure is illustrated by 24 examples in Table'll.

- TABLE II Max. Ex. Resin Amta, Amine used and Strength of Solvent used Reaction Reaction distill formaldehyde tern time No used grs, amount 80m. and mm and amt. Q (hm) hangs.

1 t 2a 882 Diethanolamine, 210 g. ..1 Xylene, 700 g. 22-26 32 147 2ba 480 Dlethanolamlne, 105 g Xylene, 450 g 21-23 28 150 3b- 1011 G33 Diethanolamine, 105 g Xylene, 600 g 20-22 36 '145 4b.- 2a 441 Dlpropanolamlne, 133 g Xylene, 400 g 20-23 34 1'46 51L 5a 480 Dipropanolamlne, 133 g Xylene, 450 g 21-23 24 141 6b. 1. a 633 Dipropanolamlne, 133 g Xylene, 600 g. 21-28 24 145 7b. 2a 882 Ethylethanolamlne, 178 Xylene, 700 g 20-26 24 152 8b. 5a 480 Ethylethanolamlne, 89 g. Xylene, 450 24-30 28 151 9b.. 10a 633 Ethylethanolamine, 89 g 22-25 27 147 100. 130 473 Cyclohexylethanolamine, 143 g..-. 21-31 31 146 11b. 14a 511 Cyclohexylethanolamlne, 143 g I 3 36 148 12b. 15a 665 Oyclohexylethanolamlne, 143 g -24 27 52 13b. 2a 441 .C9H5OCgH4OCzH4 NH, 176 g. 37%, 81 g Xylene, 400 g. 21-25 24 150 140. 5a 480 CgHaOCgH4OCzH4 v H, 176 g. 37%, 81 g Xylene, 450 g 1 20-26 26 146 HOCQH] I 1512. 9a 595 oqmoomlocm.

NH, 176 g...- 37%, 81 g Xylene, 550 g 21-27 30 147 H 001B;

16!). 1 2a 441 HOOQHAOCHtOC/QHA N,-192 g. 37%, 81 g Xylene, 400 g 20-22 30 148 170. 1 6a 480 HOC: 4OC: 4OCzH| N, 912 g. 37%, 81,3 Xylene, 400 g.. 1 20-25 28 150 Room,

18b 1 14d 591 HOO2H0CQH4OC2H4 I N, 192 g.- 37%, 81 g Xylene, 500 g 21-24 32 149 HO 01m 19b- 22 498 HOOaHAO 0 1E1 0 CgHt I I N, 192 g 37%, 81 g Xylene, 450 g 22-25 32 153 H0011]; an.' 2311 542 CH:(OC:H|)$

N, 206 g 30%, 100 g.- Xylene, we 3 21-23 as 151 HOO H 2l.b I 26a 5 47 CHa(OC1H4)a I N, 206 g 30%, 100 g Xylene, 500 3..., Y 7 -30 34 14s 22b. '2 441 CHKOCQHA)! N, 206 g long"... Xylene, 400 g 22-23 31 14s 1100,21.

23b. 26a 595 Deeylethanolamine, 201 g 37%, 81 g.' Xylene, 500 g 22-27 24 145 1b.- 171; 391 Docylethanolamine, 100 g 30%, 50 g Xylene, 300 g 21-25 26 147 PART 41 ployed. In this particular procedure the autoclave was In preparing oxyalkylated derivatives of products of the kind which appear as examples in Part 3, I have found it particularly advantageous to use laboratory equipment which permits continuous oxypropylation and oxyethylation. More specific reference will be made to treatment with glycide subsequently in the text. The 'oxyethylation step is, of course, the same as the oxypropylation step insofar that two low boiling liquids are'handled in each instance. What immediately follows refers to oxyethylation and it is understood that oxypropylation can be handled conveniently in exactly the same manner.

The oxyethylation procedure employed in the preparation of derivatives of the preceding intermediates has been uniformly the same, particularly in light of the fact that a continuous operating procedure was ema conventional jacketed autoclave, made of stainless steel and having a capacity of approximately 25 gallons, and a working pressure of 300 pounds gauge pressure. The autoclave was equipped with the conventional devices and openings, such as the variable speed stirrer operating at speeds from 50 R. P. M. to 500 R. P. M., thermometer well and thermocouple for recorder controller; emptying outlet, pressure gauge, manual and rupture disc vent lines; charge hole for initial reactants; at least one connection for conducting the incoming alkylene oxide, such as ethylene oxide, to the bottom of the'autoclavc; along with suitable devices for both cooling and heating the autoclave through the jacket. Also, I prefer coils in.

addition thereto, with the coils so arranged that they are suitable for heating with steam or cooling with water, and the jacket further equipped with electrical heating devices, such as are employedqfor hot oilor smegma:

"1'9. Dowtherm systems. Dowtherm, more specifically Dowtherm A, is a colorless --non=corrosive liquid consisting of an eutectic mixtu're of diphenyl and diphenyl oxide. Such autoclaves are, of course, in essence, "'s' iifall 's'cale replicas of the usual conventional autoclave used in commercial oxyalkylating procedure.

Continuous operation, or substantially continuous operation, is achieved by the use are separate ctj nta'iher to hold the alk lene oxide being "employed, particularly ethylene oxide The container consists essentially are. laboratory borrib having a capacity of about it) to gallons or somewhat in excess thereof. This tomb "was equipped, also, with an inlet for charging, andan outlet tube going to thebottorn of the container 'so as tofpe'riiiit discharging of alkylene oxide in the liquid phase to the autoclave. Other conventional equipmeht consists, of course, of the *rupture disc, pressure gauge, sight--feed glass, thermometer, connection for nitrogen for pres suring bomb, etc. The bomb was placed on a scale during use and the connections between the bomb and the autoclave were flexible stainless hose or tubin'g so that continuous weighin'gs could be made iwithout breaking or making any connections. This also applied to the nitrogen line, which was used to pressure the bomb reservoir. To the extent that it wa s'required'any other usual conventional procedure or addition which provided greater safety was used, of course, such as safety glass, protective screens, etc.

With this particular arrangem'ehtcpractically all oxyethylations became uniform in that the reaction temperature could be held within a few degrees of any selected point in this particular range. In the early stages where the concentration of catalyst is liig'h the temperature was generally set for around C. or thereabouts. Subsequently the temperature may instance, C. to C. Under other conditions,

definitely higher'tempera'tures may be employed, for in-- stance 170 C. to 175C. It will be noted by examination of subsequent examples that this temperature range was satisfactory. In any case,'where the reaction goes more slowly a higher teinperature'ibay be used,-for i'nstance, 140 c. to c., and if need be c. to C. Incidentally, oxypropylation takes place more slowly than oxyethylation as a rule and for this reason I have used a temperature of approximately 131) L fe 1 1i) C., as being particularly desirable for initial oxypropylation, and have stayed within the range of 130 C. to 135 C. almost invariably during oxypropylation. The lesser reactivity of propylene oxide cdnipared -with ethylene oxide can be offset by use of more catalyst, more vigorous agitation and perhaps a longer time period. The ethylene oxide was forced in by means of nitrogen pressure as rapidly as it was absorbed as indicated by-the pfsst'li'e gauge on the autoclave. In case the reaction slowed up the temperature was raised so as to speed up the reaction somewhat by use of e'xtreme 'heat. If need be,=c'ooling water was employed to' control the temperature.

As previously pointed out in the case of oxypropyla- 'ti'o'n as differentiated from oxyethylatidn, there was -a lt'e nde'ncy for the reac ion "to stow n' "'a'stlie temperature "dropped much below the selected ."p'oi'rit" er reaction, for instance, 135 C. -In"thisi1ist'a'nce, "the technique employed wasthe same as before, tliatis, eitlir'cddlingwater "was cut down or" steamfwas employed,"for"the a dition of propylene oxide speeaen up, or electric liat "iis'ed in addition to the "steam; in order'thaftlie '"raction proeeded' at, or hear, the selected teinpiatfirs to' be'rfia'intairied. V p K Inversely,"iftliejraction preee aed too' fast regardless "of thelparticular alkylene :oxide, "the 'ainount :6: :ractant being added, such -as ethylene oxide, was-cut -down or electrical heat was out oil-or steam 'was reduced, or-if need be,cooling water was-rumthrough both the iaeket and the-cooling coil. All'these operationsfiof courseiare depending on therequired number ofconventi'otialzgauges,

be somewhat higher for 1 check valves, etc., and the entire equipment, as has been pointed out, is --eonventional and, as far as -I am aware can be furnished by at least two firms who specialize in the manufacture of th'isliind 'of equipment.

Attention is directed to the fact that the use of glycide requires extreme caution. This is particularly true on any scaleother than smalllaboratory or semi-pilot plant operations. Purely from the standpoint "of safety in the handling of .glycidcqattention is directed to the following: ra If prepared from :gly'c'erol monochlorohydrin, thisgproduct shouldbe comparatively pure; (b) the glycide itself "should be as jpure 'a's possible as the efieet of impurities-is difiicult't'o "evaluate; =(c) the glycide should be introduced carefully anil'pree ution should be taken that it reacts as promptly as introduced, i. e., that no excess of glycide is allowed to aeeumutateyw all "necessary precautions should *be taken that glycide cannot polymerize per se; (0) dueto thehigh boiling poirit of glycidc one can readily employ a typical separatable glass resin pot as described in U. S. Patent No. 7,499,370 dated March 7,"-l-950, 'and=oiiered for sale by numerous laboratory supply houses. Ifsuch arrangem'ent is used to prepare laboratory scale duplications, then care should be taken that the heating mantle canbe removed rapidly so astoallow fdr eooling; or better still, through an added opening at the top, the :glass resin pot or comparable vessel should be equipped with a stainless steel cooling coil so that the pot canbe cooled more rapidly'than mere removalermanne. If a stainless steel coil is introduced it means that conventional stirrer of the paddle type is changed into the centrifugal type which causes the fluids or reactants to mixdue fo'svvirling a'cti'on in the center or the' pot. Still better, is the use of a laboratory autoclave of the kind previously-described in this part of thetext, but in any event, when the initial amount of glycide is added to a suitable'reactant, such as' the herein described 'ainine 'modified phenol-aldehyde resingthe speed of reaction should be controlled by the usual factorsfisuch as (a) the addition of glycide (b) the elimination of external heat, and (c) useof cooling coilso there'is no undue rise in temperature. 'All the foregoing is merely conventional but is included duet'othedlazard in handling glycide.

Although ethylene oxide and propylene oxide may represent' less of a hazard "than glycide,iyet these reactants should "be 'lrandied "with extreme care. One suitable procedure involves the use ofl pi-opylene oxide or butylene oxide as a solvent as well as-a reactaut in'the earlier stages along with ethylene oxide, for instance, by dissolving t'lie"'apprdpriate'resin'condensate in propylene oxide-even though oxyalkylation is taking place to a greater or lesser degree. After a solution has -been-obtained which represents the selected resin condensate dissolvetl in prrspytene oxidebrbut'ylene oxide, or a mixture which includes the oxyalkylated product, ethylene oxide is added to react With the-liquid mass until hyiirophileproperties are obtained, if notrpreviously "present to the desired degree. -Indeed hydrophile character --ean -be reduced or balanced by use of some other oxide such as propylene oxide or butylene oxide. Since ethylene oxide is more reactive than propylene oxide-or butylene oxide, the linal product may contain some urireaeted propylene oxide or butylenepXide which can be eliminated by volatilize- =tion ordistillation in any-suitable manner. 'See-article entitled f-Ethylene -oxide hazards and methods of thandling, Industrial and Engineering Chemistry, volume 42,-No.-6, June -l950, pp.-1251-1258. "Qtherzprocedures can-be employed as, tor-example,- that described: in U. S. .Patent No. 2-,-586,767; dated February19,1952, "to Wilson.

the onerzpreviously described and design'atedras Example -lb. "Condensate 1b"was in turn obtainedrfromidiethanol- 'antine and the resin previously identifled as-Examplefla.

Reference to Table I shows that this particular resin is obtained from paratertiarybutylphenol and formaldehyde. 11.16 pounds of this resin condensate were dissolved in 7 pounds of solvent (xylene) along with one pound of finely powdered caustic soda as a catalyst. Adjustment was made in the autoclave to operate at a temperature of approximately 125 C. to 135 C., and at a pressure of about 15 to 20'pounds.

The time regulator was set so as to inject the ethylene oxide in approximately two hours and then continue stirring for a half-hour or longer. The reaction went readily and, as a matter of fact, the oxide was taken up almost immediately. Indeed the reaction was complete in' less than an hour. More specifically it was complete in 45 minutes. The speed of reaction, particularly at the low pressure, undoubtedly was due in a large measure to excellent agitation and also to the comparatively high concentration of catalyst. The amount of ethylene oxide introduced was equal in weight to the initial condensation product, to wit, 11.16 pounds. This represented a molal ratio of 25 moles of ethylene oxide per mole of condensate.

The theoretical molecular weight at the end of the reaction period was 2232. A comparatively small sample, less than 50 grams, was withdrawn merely for examination as far as solubility or emulsifying power was concerned and also for the purpose of making some tests on various oil field emulsions. Theamount withdrawn was so small that no cognizance of this fact is included in the data, or subsequent data, or in the data presented in tabular form in subsequent Tables 3 and 4.

The size of the autoclave employed was 25 gallons. In innumerable comparable oxyalkylations I have withdrawn a substantial portion at the end of each step and continued oxyalkylation on a partial residual sample. This was not the case in this particular series. Certain examples were duplicated as hereinafter noted and subjectcd to oxyalkylation with a different oxide.

Example 20 This example simply illustrates the further oxyalkylation of Example 1c, preceding. As previously stated, the oxyalkylation-susceptible compound, to wit, Example 1b, present atthe beginning of the stage was obviously the same as at the end of the prior stage (Example 10), to wit, 11.16 pounds. The amount of oxide present in the initial step was 11.16 pounds, the amount of catalyst remained the same, to wit, one pound, and the amount of solvent remained the same. The amount of oxide added was another 11.16 pounds, all addition of oxide in these various stages being based on the addition of this particular amount. Thus, at the end of the oxyethylation step the amount of oxide added was a total of 22.32 pounds and the molal ratio of ethylene oxide to resin condensate was 50.8 to 1. The theoretical molecular weight was 3348.

The maximum temperature during the operation was 130 C. to 135 C. The maximum pressure was in the range of to pounds. The time period was one hour.

Example 30 The oxyethylation was continued and the amount of oxide added again was 11.16 pounds. There was no added catalyst and no added solvent. The theoretical molecular weight at the end of the reaction period was 5580. The molal ratio of oxide to condensate was 101.6 to 1. Conditions as far as temperature and pressure were concerned were the same as in previous examples. The time period was slightly longer, to wit, 3%. hours. The reaction unquestionably began to slow up somewhat.

Example 5c The oxyethylation continued with the introduction of another 11.16 pounds of ethylene oxide. No more solvent was introduced but .3 pound caustic soda was added. The theoretical molecular weight at the end of the agitation period was 6696, and the molal ratio of oxide to resin condensate was 127 to 1. The time period, however, dropped to 1% hours. Operating temperature and pressure remained the same as in the previous example.

Example 60 The same procedure was followed'as in the previous examples except that an added ,4; pound of powdered caustic soda was introduced to speed up the reaction. The amount of oxide added was another 11.16 pounds, bringing the total oxide introduced to 66.96 pounds. The temperature and pressure during this period were the same as before. There was no added catalyst and also no added solvent. The time period was 2 /2 hours.

Example 70 The same procedure was followed as in the previous six examples without the addition of more caustic or more solvent. The total amount of oxide introduced at the end of the period was 78.12 pounds. The theoretical molecular weight at the end of the oxyallcylation-period was 8928. The time required for the oxyethylation was a bit longer than in the previous step, to wit, 3 hours.

Example This was the final oxyethylation in this particular series. There was no added solvent and no added catalyst. The total amount of oxide added at the end of this step was 89.28 pounds. The theoretical molecular weight was 10,044. The molal ratio of oxide to resin condensate was 203.2 to one. Conditions as far as temperature and pressure were concerned were the same as in the previous examples and the time required for oxyethylation was 4 hours.

The same procedure as described in the previous ex amples was-employed in connection with a number of the other condensates described previously. All these data have been presented in tabular form in a series of four tables, Tables III and IV, V and VI.

In substantially every case a 25-gallon autoclave was employed, although in some instances the initial oxyethylation was started in a 15-gallon autoclave and then transferred to a 25-gallon autoclave. This is immaterial but happened to be a matter of convenience only. The solvent used in all cases was xylene. The catalyst used was finely powdered caustic soda.

Referring now to Tables III and IV, it will be noted that compounds 10 through 40c were obtained by the use of ethylene oxide, whereas 410 through 806 were obtained by the use of propylene oxide alone.

Thus, in reference to Table III it is to be noted as follows.

The example number of each compound is indicated in the first column.

The identity of the oxyalkylation-susceptible compound, to wit, the resin condensate, is indicated in the second column.

The amount of condensate is shown 'in the third column.- v

Assuming that ethylene oxide alone is employed, as happens to be the case in Examples is, through '40s, the amountof oxide present in the oxyalkylation derivative is shown in column 4, although in the initial step since .no oxide .ispresent there is afhlank.

When ethylene oxide is used exclusively the umn is blank.

The :Gthcolumn shows the amount of powdered caustic soda used as a catalyst, and the 7th column shows the amount of solvent employed.

The 8th column can be ignored Where a single oxide was employed.

The 9th :column shows the theoretical weight at the end of the :oxyalkylation period.

The 10th column states the amount "of condensate present in the reaction mass at the end of the period.

As pointed out previously, in 'thisiparticular series the amount of reaction mass withdrawn for examination was so small that it'was ignored andforthisreason the resin condensate in column 10 coincides with the figure in column 3.

Column 511 shows the amount of ethylene oxide employed in the reaction mass at the :end of the particulat-period.

Column 12 can be ignored insofar thatno propylene oxide wasemployed. 1

*Column 13 shows the catalyst at the end of the re action-period.

Column 14 shows the amount of solvent at the end of the reaction period.

Column 15 shows them'olal ratio of ethylene oxide to condensate.

Column 16 can be ignored 'for the reason that no propylene oxide was employed.

Referring now to Table VI. It is to be noted that the first column refers'to Examples 1e, 2e, 3e, etc.

The second -column 'gives the "maximum temperature employed during the *oxyalkylation step 'and the third column gives themaximum pressure.

The fourth column gives the time period employed.

The last three columnsshow'solubility tests by shakingasmall amount of theicompound, including the solvent present, with several volumesof water, xylene and kerosene. It sometimes happens that although "xylene in-comparatively .small amounts will dissolve in the concentrated material, when .the concentrated material in turn is diluted with xylene separation takes-place.

5th colmolecular Referring to Table IV, Examples 410 through:80c--are thecouuterparts of Examples 10 through 400, except that the oxide employed is propylene oxideinstead of ethylene oxide. Iherefore,.as explainedpreviously, fourcolumns are blank,.to' wit, columns-4, 8, 1.1 and 15.

Reference is now made to Table V. It is to be noted these compounds are designated by 'fd .numbers, 151, "221, 3d, etc., through and including 32d. They are derived, in turn, from compounds inthe e seriesnfor'example, 35c, 39c, 53c, and 62c. These compounds involve the use of both ethylene oxide and: propylene oxide. Since compounds lc through 400 were obtained by the use of ethylene oxide, it isobvious-thatthose obtained from 35c, and 390, involve the use of ethylene oxide first, and propylene oxide afterward. Inversely, these compounds obtained from 53c and 62c obviously came from a prior sericsain which propylene oxide wasuscd first.

In' the preparation of this ser'ies'indicated by the small letter d," as 1d, 2d, 3d, etc., 'theinitial "6 seriessuch as 35c, 39,530, and 620, wereduplicated and the oxyalkylation stopped at the point designated instead of being-carriedfurther "as may 'have'be'en the case in the original oxyalkylation step. Then oxyalkylation proceeded by using .the' second'o xide as indicate'dby the previous :explantitionfto Wit, propylene oxide in lrl through 1621, and ethylene .oxide in 17d .through 32d, inclusive.

In examining the table beginning with hi, it willibe I24 noted that 11112 product, i. e., 35c, :consisted of the reaction product involving 11.16 :pounds :of the :resin Irondensate, 16.74 pounds of ethylene oxide, 1L0 pound .of

' caustic soda, and 7.0 pounds 'of the solvent.

It :is to be noted that :reference to the catalyst in Table V refers to :the total amount :of catalyst, i. :e., theeatalyst present from the first oxyalkylationstep .plus .added catalyst, if any. The same is true in regard .to the solvent. Reference to the solvent refers to the total solvent pres out, i. e., that from the first :oxyalkylation step plus added solvent, if any.

in this series, itwill The noted that the theoreticalmolecular weights are given prior to the oxyalkylation .step and after the .oxyalkylation step, although the value :at the end of one :step is the rvalue at the beginning of ahc next step, except obviously at "the very .start the value depends on the theoretical molecular weight at the :end of the initial :oxyalkylation step; 2i. e., .oxyethylation for 111 through .l-6d, zand-zoxypropylation for 11721 through 32d.

it will he noted also that runder the mnlal :ratio the values of both :oxides to 1118 .resin condensate are included.

The data given :in regard .to the operating conditions is substantially the same :as before and appears in Table VI.

The products resulting from ltheseproceduresnnaynontain modest amounts, :or have small :amounts, of the :sol-

ents as indicated by the figures'in the tables. If desired the :solvent may :be removed by distillation, and particularly vacuum distillation. Such distillation .alsozmay =remove traces or small amounts of zuncombined oxide, if present and volatile under .the .conditions employed.

Obviously, in the use of "ethylene oxide and :propylene oxide in-combinati'ontone need :not firstuse one oxide and d then the other, but one can mix .the .two oxides and thus obtain what :may be termed an indiiferent oxyalkylation, i. e., no attempt to selectively add one .and then 'the other, or any othcr variant.

Needless to say, one could start with ethylene oxide and then use propylenetoxide and then go back to ethylene oxide; or, inversely, start with ,propylene oxide, then use ethylene oxide, and then "go back to propylene .oxide; or, one 'could use a-combination in which butylene oxide is used along with either one of the two oxides just mentioned, or a combination of both of them.

Thecolors ofthe products 'usually vary 'fromja reddish amber tint to a definitely red, and amber. The reason is primarily that no effort is'madeto obtain colorless resins initially and the resins'themselves may be yellow, amber, or even dark amber. Condensation of a nitrogenous product invariably yields a darker product than the original resin'and usually'has a reddish color. The solvent employed, if xylene, adds nothing to the color 'but one'may use a darker colored aromatic petroleum solvent. Oxyalkyla'tion generally tends to yield lighter .colored products and the more oxide employed the lighter the color of the product. Products can .be prcparcd in which the final .color -is .a lighter amber with :a reddish tint. Such products can be decolorized by (the use of clays, bleaching chars, etc. As far as use in demulsification'is concerned, or some othertindustrial uses, there is no justification for the cost of bleaching theproduct.

Generally speaking, the amount of alkaline catalyst presentis comparatively'small'and it need not be removed.

Since the products .per seare alkaline (due to the presence of a hasie'nitregenatom, the removal .ofthe alkaline catalyst issoniewhat more difficult than ordinarily is the case for the reason that if one adds hydrochloric acid, for example, to neutralize the alkalinity one may,partially :neutralize the basic nitrogen radical .also. The preferred procedureis to' ignore the presence of the alkali unless it is objectionable or else .add astoichiometric amount of concentrated hydrochloric acid equal to the caustic soda present.

TABLE VI-Continued PART The products described in .Part 4 have utilityin at least two distinct ways-the products as such or in the form" of some simple derivative, such as the salt, which canbe used in numerous arts subsequently described. Also, the products can serve as initial materials for more complicated reactions of the kind ordinarily involving a hydroxyl radical. This includes esterification, etherization, etc. Likewise, the group including the nitrogen atom can be reacted with suitable reactants such as chloroacetic acid esters, benzyl chloride, alkyl halides, esters of sulfonic acids, methyl sulfate, or the like, so as to give new ammonium compounds which may be used, not only for the purpose herein described, but also for various other uses.

The products herein described as such and prepared in accordance with this invention can be used as emulsifying agents, for oils, fats, and waxes, as ingredients in insecticide compositions, or as detergents and wetting agents in the laundering, scouring, dyeing, tanning and mordanting industries. They may also be used for preparing boring .or metal-cutting oils and cattle dips, as metal pickling inhibitors, and for pharmaceutical purposes.

Other uses include the preparation or resolution of petroleum emulsions, whether of the water-in-oil type or oil-in-water type. They may be used as additives in connection with other emulsifying agents; they may be employed to contribute hydrotropic eflects, they may be used as anti-strippers in connection with asphalts;

.they may be used to prevent corrosion, particularly the corrosion of ferrous metals for various purposes and particularly in connection with the production of oil and gas, and also in refineries where crude oil is converted into various commercial products. The products may be used industrially to inhibit or stop micro-organic growth or other objectionable lower forms of life, such as the growth of algae, or the like; they may be used to inhibit the growth of bacteria, molds, etc.; they are valuable additives to lubricating oils, both those derived from petroleum and syntheticlubricating oils, and also to hydraulic brake fluids of the aqueous or nonaqueous type. Some have definite anti-corrosive action; they may be used in connection with other processes where they are injected into an oil or gas well for purpose of removing a mud sheath, for increasing the ultimate flow of' fluid from the surrounding strata, and particularly in secondary recovery operations using aqueous flood waters; and for use in dry cleaners soaps.

With regard to the above statements, reference is made particularly to the use of the materials as such, or in the form of a salt; the salt form refers to a salt involving either one or both basic nitrogen atoms. Obviously, the salt form involves a modification in which the hydrophile character can either be increased or decreased and, inversely, -the hydrophobe character can be decreased or increased. For example, neutralizing the product with practically any low molal acid, such as acetic acid, hydroxy acetic acid, lactic acid, or nitric acid, is apt to markedly increase the hydrophile effect. 'One may also use acids of the type in which R is a comparatively small alkyl radical, such as methyl, ethyl or propyl. The hydrophile effect may be decreased and the hydrophohc elfect increased by neutralization with a monocarboxy detergent-forming acid. These are acids which have at least 8 and not more than 32 carbon atoms. They are obtained from higher fatty acids and include also resin acids such as abietic acid, and petroleum acids such as naphthenic acids and acids obtained by the oxidation of Wax. One can also obtain new products having unique properties by combination with, pclybasic acids, such as diglycolic acid, oxalic acid, dimerized acids from linseed oil, etc. The most common examples, of course, are the higher fatty acids having generally 10 to 18 carbon atoms. 1 have found that a particularly valuable anti-corrosive agent can be obtained from any suitable resin and formaldehyde provided the secondary amine is hydroxyethyl cyclohexylamine. The corrosion-inhibiting properties of this compound can be increased by neutralization with either one or two moles of an oil-soluble sulfonic acid, particularly a sulfonic acid of the type known as mahogany sulfonic acid.

The oil-soluble sulfonic acids previously referred to may be synthetically derived by sulfonating olefine, aliphatic fatty acids, or their esters, 'alkylated aromatics or their hydroxyl derivatives, partially hydrogenated aromatics, etc., with sulfuric acid or other sulfonating agents. However, the soaps of so-called mahogany acids which are usually produced during treatment of lubricating oil distillates with concentrated sulfuric acid or higher concentration) remain in the oil after settling out sludge. These sulfonic acids may be represented as where (R) is one or more alkyl, alkaryl or aralkyl groups and the aromatic nucleus may be a single or condensed ring or a partially hydrogenated ring. The lower molecular weight acids can be extracted from the acid-treated oil by adding a small amount of water, preferably after dilution of the oil with kerosense. However, the more desirable high molecular weight (350-500) acids, particularly those produced when treating petroleum distillates with fuming acids to produce white oil, are normally recovered as sodium soaps by neutralizing the acid oil with sodium hydroxide or carbonate and extracting with aqueous alcohol. The crude soap extract is first recovered as a water curd after removal of alcohol by distillation and a gravity separation of some of the contaminating salts (sodium carbonate, sulfates and sulfites). These materials still contain considerable quantities of salts and consequently are normally purified by addition of a more concentrated alcohol followed by storage to permit settling of salt brine. The alcohol and water are then stripped out and the sodium salts so obtained converted into free acids.

Not only can one obtain by-product sulfonic acids of the mahogany type which are perfectly satisfactory and within the molecular range of 300 to 600 but also one can obtain somewhat similar materials which are obtained as the principal product of reaction and have all the usual characteristics of normal by-product sulfonic acids but in some instances contain two sulfonic groups, i. e., are disulfonic acids. This type of mahogany acid or, better still, oil-soluble sulfonic acid, is perfectly satisfactory for the above described purpose.

Much of what has been said previously is concerned 31 nhenyl or substi uted nb nyl y idyl e h of the st uc- {are in which RD represents a hydrocarbon subst t lent such .as an ,alkyl radical having 1 to ,24 carbon atoms, or a cyclic group, such as a cyclohexyl group, a phenyl group, ,or a benzyl group, and n represents .0, 1, 2 or ,3. vn is zero in the instance of the unsubstituted phenyl radical. .Such compounds are in essence oyalltylating agents and reaction involves the introduction of ,a hydrophobe group and the formation of an ,alkanol hydroxyl radical.

The compounds herein described and particularly those 5.

hyde but by the use of formaldehyde, in combination t with a carbonyl compound selected from the class of aldehydes and ketones in which there is an alpha hydrogen ,atom available as in the case of acetaldehyde or ace- .tone. ,Such resins almost invariably involve the ,use of a basic catalyst. Such bridge radicals between phenolic nuclei have either hydroxyl radicals or {carbonyl radicals, or both, and are invariably oxyalkylation-susceptible and may also enter into more complicated reactants with basic secondary amines. The bridge radical in the initial resin has distinct hydrophile character. Such resins or compounds which can be converted readily into such resins are described in the following patents. Such analogous compounds are not included as part of the instant invention.

:U.;S. Pate nts Nos. 2,191,802, dated ,February27, 1940,, to Novotny et al.; 2,448,664, dated September 27, ,1948, i Fife et 1 1 3 ,3 3 dated J n y 3 .5. .1 fichrimpe; 2,538,884, dated January 123 19 51, to 5chrimpe;.2,545,5 5 9, dated March 20, 195.1, to schrirnne; and 2,570,389, dated October 9, 1951, to Schrirnpe.

,See my co-pending applications, Serial .Nos. 301,803, 301,805, 301,806, and 30-1;807 all filed July 20, 1952.

,Having thus described my invention, what :I .claim as fnew and desire to obtain by Letters Patent, .is:

l. The process of first condensing (a) anonyallcylationsusceptible, fu sible, non-oxygenated organic solvent-sol- ,uble, water-insoluble, low-stage phenolaldehyderesin having ;an average molecular weight corresponding to ,at least 3 and not over 6 phenolic nuclei per resin .rnolecule;

.said resin being difunctional'only in regard to methyloli formingreactivity; said resin being derived by reaction .between a difunctional monohydric phenol and an aldehyde having not over 8 carbon atoms and reactive toward ,said phenol; said resin being formed in the substantial absence of phenols of functionality ,greater than ,2; said .phenol heingof :the formula in which R is an aliphatic radical having .at least 4 and notrmore than 24 carbon atoms which is .substitutedin one of the 2,4,6-positions of ,the phenolic nucleus; (b,) a

basic hydroxylated secondary monoamirie having not more than 32 carbon atoms in any .group attached-to sufficiently high to eliminate waterand below the pyro- 82 lytic point of the reactants and resultants of reaction; th molar rat o .Q the rea ent b a d c b ing a proximately 1:2:2, respectively and with the proviso that the resinous condensation productresulting irfom the e 5 be he -stable n ex a ky t uscep r a'fter qxyal t la ne t e e t n nde a prpdn t by means of an a lpha beta alkylene oxide having not more than -4 carbon atoms and selected from the class iconsisting of ethylene oxide, propylene oxide, butylene ox ide g' va de and rne hy vc d 2. The process of gfirst condensing (a) an x-yethylati nrsn ct h e fusi e, .ncnwxy en t r c s lvent- .soluhle, water-insoluble, low-stage phenol-formaldehyde resin having an average ,molecular weight corresponding to at least 3 and not over 5 phenolic nuclei per resin molecule; said rresinrbeing difunctional only in regard to methylol-forrning reactivity; said resin being derived by reaction between a difunctional monohydric phenol and form.- aldehyde; said resin being formed in the substantial Jab,- sence of phenols of functionality greater than 2; said phenol being of the rformula in whi h an l phati hy roca n ra ca h v ng at least 4 and not more than 14 carbon atoms which is substituted in one of .the 2,4, and 6-positions of ,the v e lt n cl us; t a as y r y s on y 'r nqamine h vi no mo t an 2 carbon atqm i an up tache t th a in ,n t gsen t a (c) formaldehyde; said condensation reaction being conducted at a temperature sufiiciently high to eliminate water .andfbelow the pyrolytie point'of the reactants and resultants of reaction, the molar ratio "of the reactants a and 0 being approximately :1:-2:2, respectively, with the proviso that the condensation reaction be conducted so as to produce a significant portion of the resultant in which each of the three reactants have contributed part of the ultimate molecule by virtue of a formaldehydederived methylene bridge connecting the amino nitrogen atom with a resin molecule; with the added proviso that the ratio of reactants 'be approximately 1, 2 and 2, respectively; with the 'further proviso that said procedure involve the use of a solvent; and with the final proviso that the-resinous condensation product resulting from the process be heat stable and oxyalkylation-susceptible; thereafter oxyalkylating said condensation product by means of an alpha-beta allgylene oxide having not more than 4 carbon'atoms and selected from the class consisting of ethylene oxide, propylene oxide, butylene oxide, -glycide;and methylglycide.

'3. The process of claim -1 wherein the oxyalkylation step is limited to the use of both ethylene oxide and propylene oxide in combination.

4. The process of claim 2 wherein the oxyalltylation step 'is limited to the .use of both ethylene oxide and propylene oxide in combination.

5. The product resulting from the process defined .in claim =1.

6. The product resulting from the process defined vin claim I 7. The product resulting from the process defined in claim 3.

'8. "Theproduct resulting from the process defined in claim -4. V

References Cited in. the tile of this patent UNITED {STATES PATENTS 2 ,0 ..:5 BFDSOD 9 6 32r499r3 8 ,Dc Gro ,7- 950 

1. THE PROCESS OF FIRST CONDENSING (A) AN OXYALKYLATIONSUSCEPTIBLE, FUSIBLE, NON-OXYGENATED ORGANIC SOLVENT-SOLUBLE, WATER INSOLUBLE, LOW-STAGE PHENOLALDEHYDE RESIN HAVING AN AVERAGE MOLECULAR WEIGHT CORRESPONDING TO AT LEAST 3 AND NOT OVER 6 PHENOLIC NUCLEI PER RESIN MOLECULE; SAID RESIN BEING FIFUNCTIONAL ONLY IN REGARD TO METHYLOLFORMING REACTIVITY; SAID RESIN BEING DERIVED BY REACTION BETWEEN A DIFUNCTIONAL MONOHYDRIC PHENOL AND AN ALDEHYDE HAVING NOT OVER 8 CARBON ATOMS AND REACTIVE TOWARD SAID PHENOL; SAID RESIN BEING FORMED IN THE SUBSTANTIAL ABSENCE OF PHENOLS OF FUNCTIONALITY GREATER THAN 2; SAID PHENOL BEING OF THE FORMULA 